Reaction of sodium cellulosate with mono-and difunctional epoxides in non-aqueous media

ABSTRACT

FIBROUS CELLULOSE ETHERS HAVE BEEN PREPARED BY A NONAQUEOUS PROCESS COMPRISNG PREPARING A SODIUM CELLULOSAFE WITH SUITABLE CELLULOSE I CONTENT IN PREPARATION FOR REACTION WITH AN EPOXIDE TO YIELD A DERIVATIVE GENERALLY USEFUL IN THE FIELD OF PERMANENT PRESS TEXTILES.

United States Patent REACTION OF SODIUM CELLULOSATE WITH MONO- AND DIFUNCTIONAL EPOXIDES IN NON-AQUEOUS MEDIA Ralph J. Berni, Metairie, Ruth R. Benerito, New Orleans, and Donald M. Soignet, Metairie, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed June 29, 1972, Ser. No. 267,313

. Int. Cl. D06m 13/10; C08b 11/08 US. Cl. 8-120 16 Claims ABSTRACT OF THE DISCLOSURE Fibrous Cellulose ethers have been prepared by a nonaqueous process comprising preparing a sodium cellulosate with suitable Cellulose I content in preparation for reaction with an epoxide to yield a derivative generally useful in the field of permanent press textiles.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the chemical treatment of cellulosic textiles. Specifically, this invention relates to the chemical treatment of cellulosic textiles in non-aqueous media to yield cellulosic derivatives in the form of textiles which are useful in the permanent press field. More specifically this invention relates to the preparation of a cellulose fabric which contains a suitable quantity of sodiumion to be quickly thereafter reacted with a certain epoxide.

The primary object of this invention is to provide a process for reacting monoand diepoxides with cotton cellulose.

Another object of this invention is to provide a process which attaches sodium ions to the cellulose structure at the hydroxyls so that in combination with the swelling caused by the same reagent prepares the Cellulose I lattice for reaction with epoxides thus producing a series of new ether derivatives of cellulose.

A third object of this invention is to provide new cellulosic ethers which find utility in the preparation of permanent-press textiles.

Definition: The word sodacell as employed throughout this specification has reference to a specific form of cellulose which contains specific quantities of sodium ions (Na+) in a swollen cellulose structure which contains the Cellulose I lattice.

In the prior art sodacell has been disclosed by Berni et al. in a paper bearing the title Anion-Exchange Cottons Prepared From Sodium Cellulose which appeared in Textile Research Journal, vol. 40, pp. 999-1006 (1970). Sodacell has been used recently as a substrate for the chemical modification of cotton in nonaqueous media. In

early work, fashioned after methods described by Schwenker and Pascu, and later others, sodacell fabrics wereprepared by reaction of sodium methoxide with cotton in methanol. Later research recognized the advantages of using premercerized fabric converted to Group IA metal cellulosates for further chemical modification.

Projections of this work which disclose the details of the present invention can be found in a paper by Berni et al., bearing the title Sodium Cellulosate and Diethylaminoethylcellulose as Substrates for Modification of Cotton With Epoxides. At this writing such paper is In Press in Industrial and Engineering Chemistry-{roduct 3,829,290 Patented Aug. 13,

7 Now we have discovered that certain sodium cellulosates prepared by reacting methanolic solutions of sodium methoxide with solvent exchanged cottons and othercel lulosic materials will provide the suitable form of Cellulose I lattice in the cotton or other textile to cause the reaction of these derivatives with certain ,epoxides.

. Many difunctional epoxides were reacted in c ncentrations of from 0.28 to 1.70 moles/liter of solution in tertiary butanol or in perchloroethylene in the process of investigation. The degree of substitution (D.S.) accomplished ranged from about .01 to .08. Most of the investigative work was carried out using cotton fabric to provide suitable material for textile testing.

In general the present invention can best be described as a process for preparing fibrous cellulose ethers which yield textile products, many of which are suitable for permanent-press garments and other household goods, the steps of the process comprising:

(a) Preparing a sodium ccllulosate with Cellulose I lattice containing about from 0.1 to 3 milliequivalents of sodium ion per gram of cellulose,

(b) Immediately thereafter reacting the sodium cellulosate of step (a) with an epoxide selected from the group consisting of:

allylglycidyl ether,

butadiene diepoxide,

butadiene monoepoxide, diglyeidyl ether of 1,4-butanediol, diglycidyl ether of glycerol, diglycidyl ether of ethyleneglycol, epichlorohydrin,

glycidyl methacrylate,

octadiene diepoxide,

phenyl glycidyl ether, and vinylcyclohexene diep'oxide in organic solvent selected from the group consisting of:

perchloroethylene, and tertiary butanol for about from 3 to 17 hours, at about from 25 to C., using the lower temperatures with the longer periods of time, to produce a fibrous cellulosic ether derivative having a degree of substitution of about from .01 to .08.

By the process of the present invention reaction of monoand diepoxides with cotton cellulose and/or cellulose derivatives such as viscose rayon, ramie, dialdehyde'cotton, partially acetylated cotton, and carboxymethylated cotton can be carried out by subjecting the selected material to treatment with a swelling agent and reacting with sodium methoxide in methanol in order to attach Na+ to the cellulosic hydroxyls. While the sodium cellulosate of the selected cellulosic material is still deprived of oxygen and all contact with water then it is reacted with the selected epoxide. Resiliency and/or increased elongation is developed in the fibers so that a fabric pre- There is, however, an alternate step to the process of this invention. That step includes the strengthening of the fiber by a pretreatment with 23% sodium hydroxide and solvent exchanging the water out prior to step (a) of the process. 2

, Resilience, as viewed here, is the ability to recover from deformation and particularlyas it applies to a quality or the property of fabrics. Whether or not a given chemically treated cellulosic material exhibits this property can best be evaluated by one of the several available physical tests commonly employed in textile testing labo-, ra'tories. The Monsanto 'Wrinkle Recovery Test was chosen here. This particular test measures the crease angle 3 :2 a I a gf-fabrics, as.a criterion for evaluation of resiliency ir'nbleached','"'was placed" in a reaction tube equipped with Paffd h e f r' sThis tes sfq y. tless b d. aainle angaq gyt g i9g1 1 s an s s- Ab u .0 iiillitit'df "Kifir'ican'Society for Testin'g Materials' "inlio'f'd'ry dimethylformarni de (DMF) was added to the Designation D1295-60T. j vessel and the fabric was allowed to swell for 16 hours. Those skilled in the art feel that the fconditioned The DMF solution was,;then-allowed to drain, and dry wrinkle fieccjSve'i-yangleshould be at least '25 0 ""(warp methanol -was added-.-and drained three: times to remove plusfilli ng before itcanbe said to be 're'silient' to the DMF and-final traces-foifiwater. 1 I p lowes'facceptable degree; A methanolic solution (3,0Q'ml.) ofjsodiummethoxide Prior art processesfor' thetreatment of cellulose with (ca. 1 molar) was added to'the'vessel and the fabricwzis' mono-and j'diepoxid'es employ cellulose pretreated with 0 allowedto react for .75 :rninu'tes while dry nitrogen was aqueoussodium hydroxide and with immediate immjerbubbled through" the' chambeiz' Thesodium methoxide si on into carb'ontetraehloride' "solutions ofonly one 'epoxsolution was drained and three 30911111." additions oft-butaidefbuta'dierie diepoxide, giving a product with increase n01 w'ereused to remove excess sodiuin methoxide and solwet and dry resiliency. Prior art processes require good vent. The t-butanol and'the fabriccould be allowed" to selubility 0f the ePOXide p y in aqueous basic S01I1- stand under dry nitrogenforvindefinite periods before retion. This seriously limits the scope of the epoxides that action, if- H I canbe employed. The process of the present invention earl Using the preferred method, the fabric was. remov d utilrzeany number of non-aqueous solvents, including from the chamber, small s't samples removed primarily t-bu tanol or perchloroethylene, which are excellent solvents for innumerable epoxides. The use of 0 these solvents'allows finishing either completely or partially free from water systems which add to ollution problems. Solvent finishing with this type process can be gbutanol vfhlch i g f ia m an .oyen g 1 accomplished with almost complete recovery of solvent T 6 gm Hated cyhn er .contammg t used. action mixture was then placed back In the oven for 4 APPLICABLE EQUATIONS hours (1) Preparation of Sodium cellulosate. The fabric was then removed, neutralized with 5% acetic acid solution, rinsed 3 times in methanol, and N50 CHE/0330B m washed for minutes in 60 C. tap water to remove all unreacted materials. The fabric was then ironed dry, al-

lowed to equilibrate for 4 hours and weighed. The fabric for titration of Na+ Contennand then,the sodacell was placed in a graduated cylinder (250 ml. used) containing 30 grams of the diglycidyl. ether of glycerol dissolved in Cellulose-0N9. 01130 30 (2) Reaction of the sodacell Wlth an epoxlde: had a weight add-on of 14.3%. The original sodacell (a) Vbutanol had a Na+ content of, 1.06 meq./g. of fabric, Th f b i Cellulose-ONa RC-C had a conditioned (dry) and wet wrinkle recovery of 21 271 and 264", respectively (warp'and fill). The fabric (Wmomepoxide) maintained 60% of its original breaking strength and Cellu1oseOC-(;J-R essentially all of 6.3% elongation at break.

, (b) (cellulose ether) 40 E MPLE 2 I t-butanol Th followin xam l" Cellulose-OI C O R C o e g e p es are shown to illustrate that butadiene dlepoxrde and epichlorohydrm srgnlficantly 1m- 0 prove dry wrinkle recovery and that other epoxides, alp though they etherify cotton, do not significantly improve Cel1u1ose-OCCRC-COCe1ll1105e dry wrinkle recovery to above permanent press minimum OH OH acceptable levels at these addons. Fabrics were treated (cellulose ether) as in Example 1 with exceptions as noted in thetable. Wrinkle IBGOVBI'Y 51 +1?) B in El egress rea ng 011 .8. Na, Add-on, strength b eak Epoxlde (30 g./250 ml.) meq./g. percent Dry. Wet (lbs.) (percent) Butadiene diepoxide 1.05 18. I 284 I 233' 22.5 4. Epichlorohydrin 1. 04 4: 9 255 222 18. 1 6. Butadiene monoepoxide... 1. 16 2. 3 196 174 35. 9 9. 8 Allyl glycrdyl ether 1. 07 4 9 186 178 27. 1 v 10. 4. Vinylcyclohexene diepoxlde. ,1. 11 1.7 205 192 80. 6 Y 1 8. 7 Diglycidyl ether of 1,4-butanediol 1. 00 8. 9 240 209 23. 4 6.7 Phenyl glycrdyl other... 1. 05 8. 2 204 180 33. 9 8. 6 Glycidyl metheerylatm. .1. 05 7.1 223 177' 28.6 92 Control 1 189 176 45.6 6.9

1 Epoxide dissolved in 250 m1. (total volurne) t-butanolat C. and reacted for 4 hrs. 1 'Mrlhequrvalents of sodium ion per, gram of fabric. V

The following examples are provided to illustrate the' i If I f 31' I invention and should not'b .--r-. 1 Y H imgmion x y'wf n ig f as i n s 10 -The followmg examples are shown to illustrate that the I; I drglycidyl-aether of glycerol-is the preferred epoxide-to will EXAMPLE sllflmficatrtrltly lmprove dryandwrinkle recovery-when perc oroe yene is used as solvent in place of t-butanol sampleoi 30 cotton printcloth werghing approxrv as in Example 1. Other jepoxides used etherified cotton 1T1 Y' Q' V 5 e beenedeslled, scoured, and, but. did" not increase wet or'dry-wrinkle recovery to minishown inthe following-tablez.

lulosic fibrous material with a methanolie solution of sodium methoxide, and

Wrinkle recovery d w+F) B ki El t a egrees rea ng ong. a

Na+ Add-on, strcn th break Epoxide (30 g./250 rnl.) meq./g 1 percent Dry (Ilia) (percent) Digiycidyl ether of glycerol- 0. 70 26. 7 274 265 32. 7 2 Butadienediepoxidei. 0. 71 19. 4 239 195 26. 9 Epichlorohydrin 0.67 4. 6 243 211 24. 8 6. 3 Drglycidyl ether of 1,4-butaned1ol- 0. 76 12. 8 243 198 31. 2 7. 2 Octadiene diepoxide.' ....--i V 0- 72 9 219 208 28. 6. 7

h. u1r1poxide (30 'g.) dissolved in perchloroethylene (250 ml. total volume) at 70 C. Fabrics were reacted for 3 I Milliequivalents of sodium ion per gram of fabric.

The following examples are shown to illustrate that (b) immediately thereafter reacting the sodium cellulosate of step (a) with an epoxide selected from the group consisting of:

high wet wrinkle recovery could be obtained with the 20 epoxides when- 23% NaOH'is used as swelling solvent ylglycidyl ether, with the use of 5 solvent exchanges of methanol to rebutadfene dlepoxlde. move final traces of water, and 0.6 M N aOCH for prepabutadlemi monoepoxlde, ration of sodacell as in Example 1 with some exceptions dlglycldyl ether of 1,4-b11tal1edi01, listed in the following table: diglycidyl ether of glycerol,

Wrinkle recovery +F) degrees Breaking Elong. at Na,+ Add-on, strength break Epoxide (30 g./250 ml.) meqJg. percent Dry (lbs.) (percent) Diglycidyl ether of glycerol 1. 53 40. 0 231 290 30. 8 19. 7 Butadiene diepoxide 1. 76 38. 8 256 265 18. 3 14.1 Epichlorohydrin 1. 54 8. 8 228 267 18. 0 20. 4 Vinyl cyclohexene diepoxide- 1. 44 6. 0 165 267 41. 0 27. 3 Diglycidyl ether of 1,4-butanedio 1. 41 18. 0 197 309 25. 2 22. 7 Glycidyl methaerylate 1. 39 15. 0 174 260 41. 3 26. 8 Phenyl glycidyl ether 1. 57 15. 7 179 224 47. 2 25. 8 Allyl glycidyl ether... 1. 47 11. 7 135 198 42. 8 31. 2 Butadiene monoeporn 1.48 7.0 161 247 49.3 29.3 Control (untreated) 189 176 45. 6 6. 9 Control (23% N 21011) 184 206 57. 3 28. 7

l Epoxide dissolved in 250 ml. (total volume) of t-butanoi at 70 C. and reacted for 4 hours.

3 Milliequivalents of sodium ion per gram of fabric.

diglycidyl ether of ethylene glycol,

EXAMPLE 5 Fabrics treated as in Example 4 with the exception that 45 p hlorohydnn, perchloroethylene was used as solvent for the epoxides y y Q Y used and the reaction time and temperature varied as octadiene diepoxrde, shown in the following table: phenyl glycidyl ether, and

Reaction conditions Wrinkle recovery (W+F) Breaking Elong. Weight Na Time Temp, Add-on, strength, at break Epoxide compound (grams) meqJg. (hr.) 0.) percent Dry Wet Obs.) (percent) Diglycidyl ether of glycerol 30 1- 1 3 70 41. 9 232 265 32. 4 19. 8 1. 40 0. 5 105 9. 7 219 253 36. 0 6. 9 1. 40 0. 5 105 11. 7 233 227 34. 9 6. 1. 0. 5 105 11. 8 255 244 38. 6 6. 30 1. 40 17. 0 30 12. 5 198 219 39. 6 8B.

Epichlorohydrin 30 21 3 9. 5 214 267 27. 1 22.

Diglycidyl ether of 1,4-butanedi0l 3 1- 22 3 70 27. 0 220 249 34. 1 21. 10 1. 40 0. 5 5. 9 196 206 38. 7 7. 20 1. 40 0. 5 105 7. 9 235 38. 1 7. 30 1. 40 0. 5 105 8. 8 221 210 40. 5 7.

Diglycidyl ether of ethylene glycol.... 30 1- 4 0. 5 105 13. 3 236 206 30. 6 7. Oetadiene diepoxide 30 1- 19 3. 0 70 14. 3 205 292 24. 5 21. Con trnl 189 176 47. 4 9.

1 Grams of epoxide in 250 ml. of perchloroethylene solution. Milliequivalents of sodium ion per gram of fabric.

We claim:

70 vmyleyclohexene diepoxrde 1. A process for preparing under anhydrous conditions fibrous cellulose ethers which yield textile products, the process comprising:

(a) preparing a sodium cellulosate with Cellulose I lattice containing about from 0.1 to 3 milliequivalents of sodium ion per gram of cellulose by reacting a cela fibrous cellulosic ether derivative having a degree of substitution of about from .01 to .08.

2. The process of Claim 1 wherein the epoxide is allylglycidyl ether.

*3. The process of Claim 1 wherein the epoxide is butadiene diepoxide.

4. The process of Claim 1 wherein the epoxide is butadiene monoepoxide.

5. The process of Claim 1 wherein the epoxide is diglycidyl ether of 1,4-butanediol.

6. The process of Claim 1 wherein the epoxide is diglycidyl ether of glycerol.

7. The process of Claim 1 wherein the epoxide is diglycidyl ether of ethylene glycol.

8. The process of Claim 1 wherein the epoxide is epichlorohydrin.

9. The process of Claim 1 wherein the epoxide is glycidyl methacrylate.

10. The process of Claim 1 wherein the epoxide is octadiene diepoxide.

11. The process of Claim 1 wherein the epoxide is phenyl glycidyl ether.

12. The process of Claim 1 wherein the epoxide is vinylcyclohexene diepoxide.

13. The process of Claim 1 wherein the solvent is perchloroethylene.

8 14. The process of Claimfl wherein the solvent is terti: ary butanol. 15. The allylglycidyl ether of cellulose prepared by the process of Claim 1.

16. The butadiene ether of cellulose prepared by the process of Claim 1.

References Cited UNITED. STATES, PATENTS, *3 3,293,073 12/1966 Goodman et a1. *"'8 12'0 X 3,372,977 3/1968. Berni et a1. 8-120, OTHER gasannlscizs f Berni et al.: article in-Textile Research Journal, vol. 40, No. 11, November 1970, pp. 999-1006.

McKelvey et al.: article in Textile Research vol. 29, 1959, pp. 918-9 25. Avney et al.: article in Textile Research Journal, vol. 38, 1968, pp. 599-605. :1 1'

HERBERT B. GUYNN, Primar y was i Journal, 

